CN107150463A - A kind of metal-resin composite and its preparation technology - Google Patents
A kind of metal-resin composite and its preparation technology Download PDFInfo
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- CN107150463A CN107150463A CN201710411242.3A CN201710411242A CN107150463A CN 107150463 A CN107150463 A CN 107150463A CN 201710411242 A CN201710411242 A CN 201710411242A CN 107150463 A CN107150463 A CN 107150463A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions
- B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
- B32B3/085—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts spaced apart pieces on the surface of a layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/162—Cleaning
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/04—Punching, slitting or perforating
- B32B2038/047—Perforating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/554—Wear resistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/718—Weight, e.g. weight per square meter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Abstract
The present invention proposes a kind of metal-resin composite and its preparation technology, including aluminium alloy layer, and the aluminium alloy layer is provided with first anode oxide-film, and the first anode oxide-film is provided with second plate oxide-film；Containing on the first anode oxide-film includes outer layer and internal layer on second plate oxide-film described in the first nano-pore, contain etch pit on the outer layer, contain the second nano-pore on the internal layer, second oxide-film is provided with resin bed, and the resin material of resin bed is filled with first etch pit and the second etch pit, this complex has used modified polyetheretherketonematerials materials to be combined with aluminum alloy materials, and obtained complex performance is preferable, and lighter weight；And use two layers of anodic oxidation membrane structure, coordinate microetch technique twice, it is ensured that sufficiently large in the aperture of the nanometer micropore of the oxide layer of internal layer, the nano-pore of outer layer will not cause aperture excessive because of multiple corrosion, it ensure that resin material can be entered in nano-pore, increase adhesion.
Description
Technical field
The present invention relates to field of compound material, more particularly to a kind of metal-resin composite and its preparation technology.
Background technology
In the part manufacture field of automobile, household electrical appliance product, industrial machine etc., it is desirable to the one of metal and resin into
Type technology, current industry using adhesive under normal temperature or heating by combination that metal and synthetic resin are integrated.Using above-mentioned
The complex metal obtained although method can prepare metal and integrally moulded complex according to these methods and modeling
Adhesion is poor between glue, and adhesive acid-fast alkali-proof poor performance, and complex can not be carried out at the surfaces such as follow-up anodic oxidation
Reason.Thus, all the time, people are examining whether the engineering resin of high intensity and aluminium alloy etc to have always more reasonably
The method of alloy integration.
Those skilled in the art is by having researched and proposed nanoprocessing treatment technology, nanoprocessing treatment technology (NMT)
It is exactly metal combination technology integrated with plastic cement, it allows plastic cement directly in metal surface by the way that metal-surface nano is handled
Upper ejection formation, makes metal can be with integrated molding with plastic cement.For effective combination of metal and plastic cement, nanometer forming technique is
A kind of best methods, and insertion conventional at present can be replaced to project or zinc-aluminium, magnalium die casting, a kind of tool can be provided
There are price competition, high performance gold modeling integration product.Compared with bonding technique, NMT technologies have obvious advantage, for example：
Reduce overall weight, excellent strength, processing efficiency height of product etc..NMT technology applications cover vehicle, information technoloy equipment and 3C productions
Product, can allow product to develop towards more frivolous, more miniature direction.
And in the prior art, such as patent announcement number is：The A of CN 103290449 patent of invention, it discloses a kind of surface
The aluminium alloy of processing and its method for surface treatment and aluminum alloy resin complex and preparation method thereof, the aluminium alloy bag disclosed
Internal layer and layer structure are included, and the hole of two kinds of different pore sizes can be formed and is combined with resin material, and this kind of structure is used, it is many
In secondary immersion etching solution so that two kinds of different apertures of oxidation layer surface formation, the problem of technique is present is：Due to repeatedly leaching
Steep the aperture of uncontrollable each micro molding, after internal layer aperture is up to standard, the aperture of outer layer is increasing, and cause resin with
Its adhesion is reduced, and needs repeatedly dipping, and the time is 60 minutes or so, and elapsed time is longer.
And for example publication No. be the A of CN 102268183 patent of invention, the complex of disclosed aluminum or aluminum alloy and plastics and
Its preparation method, has used the mechanism of individual layer, although nanometer micropore, but using existing general material of reporting for polyphenylene sulfide
(PPS), polyamide (PA), polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) (PBT) plastics, on
The material stated is the common plasticses of this area, but the mechanical strength of itself is general, and density is not small enough, causes product head is made
First adhesion reduction, while product quality is not light enough, influence vehicle, information technoloy equipment and more frivolous, the more miniature direction hair of 3C Product
Exhibition.
The content of the invention
In order to solve the above technical problems, the present invention proposes a kind of metal-resin composite, including aluminium alloy layer, the aluminium
Alloy-layer is provided with first anode oxide-film, and the first anode oxide-film is provided with second plate oxide-film；First sun
Contain the first nano-pore on the oxide-film of pole, the aperture of first nano-pore is 30nm-60nm；On the second plate oxide-film
Including outer layer and internal layer, etch pit is contained on the outer layer, the etch pit is to be received on 1 μm -50 μm, the internal layer containing second
Metre hole, the second nano-pore aperture is 30-60nm, and second oxide-film is provided with resin bed, and first etch pit
With the resin material that resin bed is filled with the second etch pit.
It is preferred that, the resin material includes following component：5-10 parts of polyether-ether-ketone, 2-3 parts of carbon fiber, titanium dioxide 1-
3 parts and 0.6-1 parts of tantalum element.
It is preferred that, the thickness of the first oxygen anodes oxide-film is 1 μm -5 μm, and the hole depth of first etch pit is 0.5 μ
M-19.5 μm, the thickness of the second plate oxide-film is 1 μm -20 μm, the hole depth of first etch pit and the described first sun
Pole oxide-film is identical.
A kind of preparation technology of composite metal, comprises the following steps：
S1：Aluminium alloy plate surface is deoiled, and aluminium alloy is placed inDegreaser, oil removing agent concentration is 10-70g/L,
Retention time 50-500 second；
S2：Nanometer cleaning, the nanometer that concentration is 10-200ml/L will be placed in through the step S1 aluminium alloys for handling completion and will be cleaned
It is rinsed in agent, temperature control is rinsed 50-500 seconds at 10-30 DEG C；
S3：Aluminium alloy plate is subjected to first time anodic oxidation reactionses, aluminium alloy plate surface forms first anode oxidation film layer；
S4：First time reaming is carried out to first anode oxide-film：Aluminium alloy plate in S3 is placed in micro-corrosion liquid carry out it is micro-
Erosion, concentration is 10-200g/L, is reacted while adding 10-300g ammonium acid fluorides, 10-100 DEG C of temperature, time 200-300
Second；
S5：Obtained aluminium alloy plate in S4 is carried out after nanometer flushing, second reaming is carried out, second reaming uses microporous
Inorganic agent, it is ensured that temperature is at 15-25 DEG C, processing time 400-500 second, and the 5-30V that is powered；
S6：To carrying out second of anodic oxidation reactions by the aluminium alloy plate body of second reaming, in first anode oxide-film
Upper progress two-step anodization reaction, and form second plate oxide-film；
S7：Micropore processing is carried out to second plate oxide-film, mechanical grinding is carried out first, surface forms etch pit, after again
The step of carrying out S4, S5 so that second plate oxide-film surface forms micropore；
S8：Resin material pre-treatment；
S9：The aluminium alloy plate that resin material is injected in S7 by injection machine is cooled and shaped, complex is made.
It is preferred that, pure water cleaning step is set between step S1-S7.
It is preferred that, the degreaser is the mixture of sodium phosphate, Boratex and sodium carbonate liquor, and mixed proportion is：1:3:
2。
It is preferred that, the nanometer cleaning agent is：The mixture of nitric acid and ferric trichloride.
It is preferred that, the micro-corrosion liquid is the mixture of sodium sulphate and ammonium sulfate.
It is preferred that, the microporous inorganic agent is the mixture of phosphoric acid, sulfuric acid, phthalic acid and terephthalic acid (TPA).
Anodic oxidation includes being put into the metal base Jing Guo pre-treatment as anode in concentration sulphuric acid solution, temperature 10-
30 DEG C obtain the metal base that the thick anode oxidation membranes of 1-20um are contained on surface in electrolysis 1-40min under 10V-100V voltages.
Wherein, the resin material pre-treatment comprises the following steps：
A1：Polyether-ether-ketone solution is taken in reactor, while adding titanium dioxide carries out polycondensation reaction；
A2：Continuous carbon fibre is impregnated into modified polyetheretherketonefiber resin solution, Ran Houjun with the 15-25m/min speed of service
It is even to be arranged on roller, continuous carbon fibre reinforced polyether ether ketone prepreg is made, by injection molding；
A3：During by carrying out tantalum ion injection on the surface of polyether-ether-ketone with plasma immersion ion implantation technique, use
Simple metal tantalum adds tantalum element to polyether-ether-ketone surface as negative electrode；
A4：Polyether-ether-ketone is melted it is stand-by, injection aluminium alloy plate body in.
Metal-resin composite proposed by the present invention and its preparation technology have following beneficial effect：This complex is using changing
Property polyetheretherketonematerials materials and aluminum alloy materials be combined, in itself with good wearability and mechanical property, what is obtained answers
Fit better performances, and lighter weight；And two layers of anodic oxidation membrane structure has been used, has coordinated microetch technique twice, it is ensured that
Sufficiently large in the aperture of the nanometer micropore of the oxide layer of internal layer, the nano-pore of outer layer will not cause aperture mistake because of multiple corrosion
Greatly, it is ensured that resin material can be entered in nano-pore, adhesion is increased.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, makes required in being described below to embodiment
Accompanying drawing is briefly described.
Fig. 1 is the structural representation of the composite metal of the present invention；
Wherein, 1- aluminium alloy layers, 2- first anode oxide-films, 3- internal layers, 4- outer layers.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described.
The present invention proposes a kind of metal-resin composite, including aluminium alloy layer 1, and the aluminium alloy layer 1 is provided with first
Anode oxide film 2, the first anode oxide-film 2 is provided with second plate oxide-film；Contain on the first anode oxide-film 2
First nano-pore, the aperture of first nano-pore is 30nm-60nm；Include internal layer 3 on the second plate oxide-film and interior
Contain etch pit on layer 3, the outer layer 4, the etch pit is to contain the second nano-pore on 1 μm -50 μm, the internal layer 3, described
Second nano-pore aperture is 30-60nm, and second oxide-film is provided with resin bed, and first etch pit and the second corrosion
In hole be filled with resin bed resin material, wherein the aperture of the first nano-pore and the second nano-pore can be 30nm, 35nm,
40nm, 50nm, 55nm, 60nm, three above nano aperture ensure that resin material enters, and adhesion is strong, and increase
Plus etch pit can increase the adhesive force and compactedness of resin and metal material.
Wherein, the resin material includes following component：5-10 parts of polyether-ether-ketone, 2-3 parts of carbon fiber, titanium dioxide 1-3
Part and 0.6-1 part of tantalum element, the polyetheretherketonematerials materials of selection polycondensations simultaneously tantalum element and titanium dioxide, add a small amount of tantalum first
Element so that the stability on surface is higher, and with preferable peel resistance, the density of polyether-ether-ketone itself is smaller so that gold
The quality of category complex is greatly reduced.
Embodiment 1
Take aluminium alloy plate surface to deoil, aluminium alloy is placed inDegreaser, oil removing agent concentration is 50g/L, is kept
Time 100-200 second；Nanometer cleaning, the nanometer cleaning agent that concentration is 50ml/L is placed in by the aluminium alloy completed is handled through step S1
In be rinsed, temperature control at 20 DEG C, rinse 100-150 seconds；Aluminium alloy plate is subjected to first time anodic oxidation reactionses, aluminium is closed
Golden plate surface forms 2 layers of first anode oxide-film；Above-mentioned aluminium alloy plate is placed in micro-corrosion liquid, micro-corrosion liquid carries out micro- in selecting
Erosion so that 25nm aperture is obtained in first anode oxide layer, the thickness of first anode oxide-film 2 is 5 μm, and concentration is 50g/L,
Add 100-150g ammonium acid fluorides simultaneously to be reacted, hydrogen fluoride promotes surface corrosion, temperature 70 C, time 200-300 second；
Obtained aluminium alloy plate is carried out after nanometer flushing, second reaming is carried out, second reaming uses microporous inorganic agent,
Ensure temperature at 18 DEG C, processing time 400-500 second, and the 18-28V that is powered, it is 30nm to finally give aperture.
To carrying out second of anodic oxidation reactions by the aluminium alloy plate body of second reaming, on first anode oxide-film 2
Two-step anodization reaction is carried out, and forms 5 μm of second plate oxide-film；Micropore processing is carried out to second plate oxide-film, it is first
First carry out mechanical grinding, surface forms etch pit, after carry out the processing of first anode oxide layer again so that second plate oxide-film
Surface forms micropore, and the micropore on surface forms 30nm, and the aperture of etch pit is 1 μm；
To resin material pre-treatment；
A1：Polyether-ether-ketone solution is taken in reactor, while adding titanium dioxide carries out polycondensation reaction；
A2：Continuous carbon fibre is impregnated into modified polyetheretherketonefiber resin solution, Ran Houjun with the 15-25m/min speed of service
It is even to be arranged on roller, continuous carbon fibre reinforced polyether ether ketone prepreg is made, by injection molding；
A3：During by carrying out tantalum ion injection on the surface of polyether-ether-ketone with plasma immersion ion implantation technique, use
Simple metal tantalum adds tantalum element to polyether-ether-ketone surface as negative electrode；Wherein described resin material includes following component：Polyethers
0.6 part of 5- parts of ether ketone, 2 parts of carbon fiber, 1 part of titanium dioxide and tantalum element
A4：Polyether-ether-ketone is melted it is stand-by, injection aluminium alloy plate body in.
Resin material is injected into aluminium alloy plate by injection machine to be cooled and shaped, complex is made.
It is preferred that, pure water cleaning step is set between step S1-S7.
It is preferred that, the degreaser is the mixture of sodium phosphate, Boratex and sodium carbonate liquor, and mixed proportion is：1:3:
2。
It is preferred that, the nanometer cleaning agent is：The mixture of nitric acid and ferric trichloride.
It is preferred that, the micro-corrosion liquid is the mixture of sodium sulphate and ammonium sulfate.
It is preferred that, the microporous inorganic agent is the mixture of phosphoric acid, sulfuric acid, phthalic acid and terephthalic acid (TPA).
Using plasma immersion ion injection technique, polyether-ether-ketone matrix is injected by tantalum ion, injects modified gather
Ether ether ketone material is properly preserved, and its specific technological parameter is shown in Table 1：The tantalum ion injection parameter of table 1：Injecting voltage 30KV is noted
Enter the μ s injection length 30min base vacuums 5 × 10 of pulsewidth 450-3(Pa) negative electrode triggering pulsewidth 700 (μ s), frequency 7 (Hz)
Embodiment 2
The present embodiment and the difference of embodiment 1 are, 25nm aperture, the first sun are obtained in first anode oxide layer
The thickness of pole oxide-film 2 is 10 μm, and concentration is 50g/L, is reacted while adding 150g ammonium acid fluorides, hydrogen fluoride promotes surface
Corrosion, temperature 70 C, 250 seconds time；
Obtained aluminium alloy plate is carried out after nanometer flushing, second reaming is carried out, second reaming uses microporous inorganic agent,
Ensure temperature at 18 DEG C, 450 seconds processing times, and the 18-28V that is powered, aperture is finally given for 35nm.
To carrying out second of anodic oxidation reactions by the aluminium alloy plate body of second reaming, on first anode oxide-film 2
Two-step anodization reaction is carried out, and forms 10 μm of second plate oxide-film；Micropore processing is carried out to second plate oxide-film, it is first
First carry out mechanical grinding, surface forms etch pit, after carry out the processing of first anode oxide layer again so that second plate oxide-film
Surface forms micropore, and the micropore on surface forms 35nm, and the aperture of etch pit is 1.5 μm；
Same that resin material is carried out after pre-treatment, resin material includes following component：5 parts of polyether-ether-ketone, carbon fiber 2
0.6 part of part, 1 part of titanium dioxide and tantalum element
A4：Polyether-ether-ketone is melted it is stand-by, injection aluminium alloy plate body in.
Resin material is injected into aluminium alloy plate by injection machine to be cooled and shaped, complex is made.
Embodiment 3
The present embodiment and the difference of embodiment 1 are, 25nm aperture, the first sun are obtained in first anode oxide layer
The thickness of pole oxide-film 2 is 20 μm, and concentration is 50g/L, is reacted while adding 150g ammonium acid fluorides, hydrogen fluoride promotes surface
Corrosion, temperature 70 C, 300 seconds time；
Obtained aluminium alloy plate is carried out after nanometer flushing, second reaming is carried out, second reaming uses microporous inorganic agent,
Ensure temperature at 18 DEG C, 450 seconds processing times, and the 18-28V that is powered, aperture is finally given for 45nm.
To carrying out second of anodic oxidation reactions by the aluminium alloy plate body of second reaming, on first anode oxide-film 2
Two-step anodization reaction is carried out, and forms 20 μm of second plate oxide-film；Micropore processing is carried out to second plate oxide-film, it is first
First carry out mechanical grinding, surface forms etch pit, after carry out the processing of first anode oxide layer again so that second plate oxide-film
Surface forms micropore, and the micropore on surface forms 45nm, and the aperture of etch pit is 10 μm；
Same that resin material is carried out after pre-treatment, it is unchanged that resin material includes following component：5 parts of polyether-ether-ketone, carbon are fine
0.6 part of 2 parts of dimension, 1 part of titanium dioxide and tantalum element
A4：Polyether-ether-ketone is melted it is stand-by, injection aluminium alloy plate body in.
Resin material is injected into aluminium alloy plate by injection machine to be cooled and shaped, complex is made.
Embodiment 4
The present embodiment and the difference of embodiment 1 are, 25nm aperture, the first sun are obtained in first anode oxide layer
The thickness of pole oxide-film 2 is 20 μm, and concentration is 50g/L, is reacted while adding 150g ammonium acid fluorides, hydrogen fluoride promotes surface
Corrosion, temperature 70 C, 300 seconds time；
Obtained aluminium alloy plate is carried out after nanometer flushing, second reaming is carried out, second reaming uses microporous inorganic agent,
Ensure temperature at 18 DEG C, 450 seconds processing times, and the 18-28V that is powered, aperture is finally given for 50nm, by secondary micropore
Afterwards, realize both.
To carrying out second of anodic oxidation reactions by the aluminium alloy plate body of second reaming, on first anode oxide-film 2
Two-step anodization reaction is carried out, and forms 20 μm of second plate oxide-film；Micropore processing is carried out to second plate oxide-film, it is first
First carry out mechanical grinding, surface forms etch pit, after carry out the processing of first anode oxide layer again so that second plate oxide-film
Surface forms micropore, and the micropore on surface forms 50nm, and the aperture of etch pit is 20 μm；
Same that resin material is carried out after pre-treatment, it is unchanged that resin material includes following component：5 parts of polyether-ether-ketone, carbon are fine
0.6 part of 2 parts of dimension, 1 part of titanium dioxide and tantalum element
A4：Polyether-ether-ketone is melted it is stand-by, injection aluminium alloy plate body in.
Resin material is injected into aluminium alloy plate by injection machine to be cooled and shaped, complex is made.
Embodiment 5
The present embodiment and the difference of embodiment 1 are, 25nm aperture, the first sun are obtained in first anode oxide layer
The thickness of pole oxide-film 2 is 5 μm, and concentration is 50g/L, is reacted while adding 150g ammonium acid fluorides, hydrogen fluoride promotes surface
Corrosion, temperature 70 C, 300 seconds time；
Obtained aluminium alloy plate is carried out after nanometer flushing, second reaming is carried out, second reaming uses microporous inorganic agent,
Ensure temperature at 18 DEG C, 450 seconds processing times, and the 18-28V that is powered, aperture is finally given for 60nm, by secondary micropore
Afterwards, realize both.
To carrying out second of anodic oxidation reactions by the aluminium alloy plate body of second reaming, on first anode oxide-film 2
Two-step anodization reaction is carried out, and forms second plate oxide-film；Micropore processing is carried out to second plate oxide-film, entered first
Row mechanical grinding, surface forms etch pit, after carry out the processing of first anode oxide layer again so that second plate oxide-film surface
Micropore is formed, the micropore on surface forms 60nm, and the aperture of etch pit is 50 μm；
Same that resin material is carried out after pre-treatment, it is unchanged that resin material includes following component：5 parts of polyether-ether-ketone, carbon are fine
0.6 part of 2 parts of dimension, 1 part of titanium dioxide and tantalum element.
A4：Polyether-ether-ketone is melted it is stand-by, injection aluminium alloy plate body in.
Resin material is injected into aluminium alloy plate by injection machine to be cooled and shaped, complex is made.
Embodiment 6
The present embodiment and embodiment 5 are all identical, and difference is, change resin material unchanged including following component：It is poly-
0.7 part of 8 parts of ether ether ketone, 2 parts of carbon fiber, 2 parts of titanium dioxide and tantalum element.
Embodiment 7
The present embodiment and embodiment 5 are all identical, and difference is, change resin material unchanged including following component：It is poly-
0.9 part of 10 parts of ether ether ketone, 3 parts of carbon fiber, 3 parts of titanium dioxide and tantalum element.
Comparative example 1
This comparative example is to carry out an anodic oxidation, one layer of anode of surface formation in the difference of embodiment and embodiment 1
Oxide-film, and by single-steeping such as micro-corrosion liquid, obtaining oxide-film top layer aperture 90nm, the aperture 20nm of internal layer 3.
Comparative example 2
The difference of this comparative example and embodiment 1 is that resin material selects PPS.
Comparative example 3
The difference of this comparative example and embodiment 1 is, does not add tantalum element in resin material.
The part of same volume size is taken to complex made from above-described embodiment, following detect is carried out：Weight, combination
Power.
Above-described embodiment can be seen that can draw from comparative example 1, and present invention uses the technique of bilayer anode oxide-film
Processing method, the nano-pore of the first oxidation film layer can penetrate whole oxidation film layer, after carry out again at second of anodic oxidation
Reason, obtains thicker anode oxide film, it is ensured that resin can enter in the nanometer micropore of bottom, considerably increase adhesion,
And reduce the process time.
It can be apparent from reference to other embodiment from comparative example 2, the present invention has selected modified polyimides as tree
Fat material, compared to traditional plastic material, substantially reduces the weight of whole complex.
With reference to comparative example 3, the addition step of tantalum element is reduced, the adhesion of obtained composite metal declines, tantalum member
Element carries out tantalum ion injection on the surface of polyether-ether-ketone to obtain the modified layer containing tantalum element, improves polyether-ether-ketone surface elasticity
Modulus and hardness closer to aluminium alloy hardness, while improve the associativity of polyether-ether-ketone surface and aluminium alloy, meanwhile, from contrast
Example 2 and 3 in conjunction with the embodiments 1, draws, composite metal is considerably increased fatigue performance, and tantalum element can be further
Improve the mechanical properties such as fatigue durability.
A variety of modifications to embodiment will be apparent for those skilled in the art, determine herein
The General Principle of justice can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, originally
Invention is not intended to be limited to the embodiments shown herein, and is to fit to and principles disclosed herein and features of novelty
Consistent most wide scope.
Claims (10)
1. a kind of metal-resin composite, it is characterised in that including aluminium alloy layer, the aluminium alloy layer is provided with first anode oxygen
Change film, the first anode oxide-film is provided with second plate oxide-film；Contain first nanometer on the first anode oxide-film
Hole, the aperture of first nano-pore is 30nm-60nm；Include outer layer and internal layer on the second plate oxide-film, it is described outer
Contain etch pit on layer, the etch pit aperture is to contain the second nano-pore, described second nanometer on 1 μm -50 μm, the internal layer
Hole aperture is 30-60nm, and second oxide-film is provided with resin bed, and first etch pit and the second etch pit and filled
There is the resin material of resin bed.
2. metal-resin composite according to claim 1, it is characterised in that the resin material includes following component：
0.6-1 parts of 5-10 parts of polyether-ether-ketone, 2-3 parts of carbon fiber, 1-3 parts of titanium dioxide and tantalum element.
3. metal-resin composite according to claim 1, it is characterised in that the thickness of the first oxygen anodes oxide-film
For 1 μm -5 μm, the hole depth of first etch pit is 0.5 μm -19.5 μm, and the thickness of the second plate oxide-film is 1 μm -20
μm, the hole depth of first etch pit is identical with the first anode oxide-film.
4. a kind of preparation technology of composite metal, it is characterised in that comprise the following steps：
S1：Aluminium alloy plate surface is deoiled, and aluminium alloy is placed inDegreaser, oil removing agent concentration is 10-70g/L, is kept
Time 50-500 second；
S2：Nanometer cleaning, is placed in the aluminium alloy completed is handled through step S1 in the nanometer cleaning agent that concentration is 10-200ml/L
It is rinsed, temperature control is rinsed 50-500 seconds at 10-30 DEG C；
S3：Aluminium alloy plate is subjected to first time anodic oxidation reactionses, aluminium alloy plate surface forms first anode oxidation film layer；
S4：First time reaming is carried out to first anode oxide-film：Aluminium alloy plate in S3 is placed in micro-corrosion liquid and carries out microetch, it is dense
Spend for 10-200g/L, reacted while adding 10-300g ammonium acid fluorides, 10-100 DEG C of temperature, time 200-300 second；
S5：Obtained aluminium alloy plate in S4 is carried out after nanometer flushing, second reaming is carried out, second reaming is handled using microporous
Agent, it is ensured that temperature is at 15-25 DEG C, processing time 400-500 second, and the 5-30V that is powered；
S6：Second of anodic oxidation reactions is carried out to the aluminium alloy plate body by second reaming, it is enterprising in first anode oxide-film
Row two-step anodization reacts, and forms second plate oxide-film；
S7：Micropore processing is carried out to second plate oxide-film, mechanical grinding is carried out first, surface forms etch pit, after carry out again
The step of S4, S5 so that second plate oxide-film surface forms micropore；
S8：Resin material pre-treatment；
S9：The aluminium alloy plate that resin material is injected in S7 by injection machine is cooled and shaped, complex is made.
5. the preparation technology of composite metal according to claim 4, it is characterised in that set pure between step S1-S7
Water cleaning step.
6. the preparation technology of composite metal according to claim 4, it is characterised in that the degreaser be sodium phosphate,
The mixture of Boratex and sodium carbonate liquor, mixed proportion is：1:3:2.
7. the preparation technology of composite metal according to claim 4, it is characterised in that the nanometer cleaning agent is：Nitre
The mixture of acid and ferric trichloride.
8. the preparation technology of composite metal according to claim 4, it is characterised in that the micro-corrosion liquid be sodium sulphate and
The mixture of ammonium sulfate.
9. the preparation technology of composite metal according to claim 4, it is characterised in that the microporous inorganic agent is phosphorus
Acid, sulfuric acid, the mixture of phthalic acid and terephthalic acid (TPA).
10. the preparation technology of composite metal according to claim 4, it is characterised in that the resin material pre-treatment
Comprise the following steps：
A1：Polyether-ether-ketone solution is taken in reactor, while adding titanium dioxide carries out polycondensation reaction；
A2：Continuous carbon fibre is impregnated into modified polyetheretherketonefiber resin solution with the 15-25m/min speed of service, then uniform row
On roller continuous carbon fibre reinforced polyether ether ketone prepreg is made, by injection molding in cloth；
A3：During by carrying out tantalum ion injection on the surface of polyether-ether-ketone with plasma immersion ion implantation technique, proof gold is used
Belong to tantalum as negative electrode, tantalum element is added to polyether-ether-ketone surface；
A4：Polyether-ether-ketone is melted it is stand-by, injection aluminium alloy plate body in.
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